Azo dyestuff derivatives of 6-amino-1, 3 benzodioxan



Patented July 3, 1945 3 UNITED STATES PAT azo DYESTUFF DERIVATIVES or ammo-a 1 I a V 1,-3 BENZODIOXAN it Hans z. Lecher, Plainfieldy Jan P. Goulding; Neshanic Station, and Robert P,- Parker, seiner;

ville, N. J.,iassignors toAmerican Cyanamid Company, Maine New York; N. Y., a corporation of N Drawing. Application December M43, l Serial No. 5131135 q i claims. (01. 260-152) This inventionflrelates to a new. series of azo dyestufis derived from G-amino-1;3-benzodioxan,

invention 'to produce a series of azo dyes developed from the ne w bases.

the dyestuff being obtained by 'diazotizationand coupling of N-substituted derivativesof theaminobenzodioxan in which the N-substituent is a p-amino-phenyhradicah The latter may be In general, the principal objects of the present invention are accomplished by condensin the amino lyii-benzodioxan with a para-nitro-halogenobenzene and subsequently reducing. the nitro:

group to an amino j gro up. resulting 1 new compounds, after diazoti zation and coupling;

yield dyestuffs which have the desired properties. ,Either para-nitrohalogenobenaenefor apara nitrohalogenobenzene containing, a negative substituent ortho to the halogen'i'adical may be used asa startingmaterial. These"negatiyesubstite 'uents maybe radicals such as halogen, nitro, 5 carboxy, or sulfonic radicals, the acyl radical of represented and numbered for purposes of the present invention as in which X may represent a hydrogen, halogen, nitro, carboxy or sulionic radical the acyLradical of a icarboxylic'acid, ora sulfonamide group.

The instant application relatesto the new azo dyestufis, particularly ice-colors} having novel color shades and unusual light ,fastness. The N 7 4 5 amino-phenyl-substituted i aminobenzodioxans per se comprise the subject matter of our copending application forUnited States Letters Patent, SerialvNo; 513,733, filed of even date.-

Very few aromatic amino compounds have been known which produce on diazotization and coupling with an ice-colorcoupling component strong blue to violet shades; It is one of the principal objectsof theprese nt invention'to produce a new series of ice-colors which will have these desirable shades. It is a further object of the a carboxylic acid or a sulfonamide group @In any case,,after cohdensationand reduction the product constitutes an N-pal'a-amino-phenyl-substituted aminobenzodioxan. "Therefore, asusedn'inj the instant application, the expression apara aminophenyl radical" includes not only the paraamino-phenyl radical, but also those 2"-substituted-4'-amino=phenyl groups in which the negative substituents are present.

Similarly, for the purposesofthe present inl vention, the expression fa sulfonamide radical is used to designate not only the group, but also substituted-sulfonamides. Inthe latter case; the sulfonamidegroup may be one in which either or both of the hydrogens are subsjtitutedby an alkyl or aryl radical or one in which the substituents form withthe nitrogen a heterocyclic ringsuch as a sulfonpiperidide, sulfon morpholide or the like. a i

Those para-nitrohalogenobenzenes containing it negative substituents, ortho to the halogen radical, are particularly useful. When such materials are used, condensation proceeds smoothly in aqueous media. The invention, however, is

not necessarily so limited. Condensation may I be carried out in any solvent compatible with the solubility and reactivity of the particular nitrohalogenobenzene employed. In some cases,

an anhydrous solvent such as nitrobenzene or the like is required. In some cases, also, the use of the cupriferous catalyst may be of advantage. Generally, too, itiswell to provide an acid binder such asa metal oxide, carbonate or the like.

' Reduction of the nitro to an amino group may 7 be carried out either by alkaline or by acidic reducing agents. The pH will determine whether free bases .or salts will be produced; It will be apparent thattwo'different types of salts are'possible. There may be acidsalts of the base. On

the other hand,'when anacidic substitutent such,

instant specification and claims. is therefore intended to include not only the bases themselves but also bothtypes of salts thereof.

twofdifferent iproducts. In general, use of higher temperatures, greater concentration of the base in solution,'higher mineral acid concentration and excess nitrous'acid generally lead to forma- ,tion' 015 an N-nitroso. derivative of the. diazonium salts. Lower temperature, lower acidjconcentrations-and controlled nitrousacid addition lead to. formation of the. diazonium chloride itself. In general, the N-nitroso, diazotization products .lead tothe production of different, duller. and

less desirable shades-when coupled. V The simple diazotizedproduct leads tothe'production of the more valuable and faster shades. Conversion of the N-nitroso colors to the more desirable shades is, accomplished through hydrolysis of the formerflflhis may be accomplished by heating the N-nitroso derivatives in dilute, solutions of some..alkaline material such as soda ash or the like. Reducing. agents such as sodium sulfide, sodium. bisulfiteflor their equivalents may be in-'- eluded in-the. saponificationbath todestroy nitric oxides. as they areliberated.

In their diazotiaed form,fthe bases maybe coupled either with or without a substratejto yield dyestufisor pigments of great value because of theirstrength, variety of shade and f astness properties. In particular, however, the bases of the Both types and the pigment developed by treatment with steam. v

Substantially any of the ice-color, coupling components are generally useful for production of insoluble, developed dyes, and enable the production of a variety of colors from yellow to blue.

However, for the present'purposes, the use of arylides of 2 -hydroxy-3-naphthoic acid is prefer-. able. These produce, when coupled with the diazotized bases of the present invention, the most desirable blue to violet shades. However, the invention is not necessarily so limited. Among other ice-color coupling components which produce useful products may be listed by way of example such compounds as betanaphthol, 3-amino-2-naphthol, 8-acety1amino-2- naphthol, benzoyl naphthols; pyrazolones and pyrazyl pyrazolones; hydroxy benzofluorenones;

hydroxy derivatives of phenyl' naphthylamines such as '7-hydroxy{l-naphthyl-m-hydroxyphenylam-ine; particularlythe various N-substituted amides such as 'arylides of 5,6,7,8-tetrahydro- Z-hydrOXyaB-naphthoic acid, of 2-hydroXy-3-anthroic acid, of methyl and dimethyl salicyclic acids, ofhydroxy carbazole carboxylic acids, of hydroxy benzocarbazole carboxylic acids, of hydroxy-benzoacridone carboxylic acids, of 3,7-di- Diazotization'of some bases of the present in- 1 hydroxy-naphthalene-2,6-dicarboxylic acid, of vention in mineral acid solution by nitrous acid produces, according to the conditions imposed,

hy droxy-dibenzofuran carboxylic acids, of hydroxybenzothiophene carboxylic acids, etc., and the .arylides of acetoacetic ,acid, furoyl ..acetic acid, benzoyl acetic acid, terphthabyl-bis-acetic acid and the like. The arylide group inthe cou+ pling component may be a simple aromatic group such as the radical of aniline or of an aniline derivative or of a naphthylamine, orit maybe the radical of a heterocyclic amine, such as, e. g., of an amine of the benzothiazole series or of a diamine of the diphenylene oxide or diphenylene sulfone series. v

The bases of the present invention also may be used in the preparation of water-soluble dyestufis suitable for dyeing vegetable or animal fibers. In thiscase, a great many of the cus:

.tomary phenolic or aminic coupling components may be used. The coupling component, however,

must carry at least one sulfonic group in case-the diazo componenthas none. Illustrative exam-v pics of such coupling components include sali-; cyclic acid, resorcinol, m-phenylene diamine, the

large number of naphthol-sulfonic acids such as e. g., R acid, C acid, the Cleves acids, J I acid,

Gamma acid, J-acid urea and J-acid-imide,-H

acid and many othersi Pyrazolones such as sulfonic derivatives of l -phenyl-3-methyl pyrazolone-5 also maybe used.

If so desired, the new diazo components of the I present invention also maybeused for the pro-.

duction'of dis-and poly-azo dyesin accordance with the customary procedures. a Depending vupon their structure, the dyes obtained from the new baths with appropriate ice-color coupling com v I ponents and then printing solutions of the diazotized bases which have been buffered and thickenedupon such prepared cloth,-or by paddyeing.

the prepared cloth in buffered solutions of the I diazotized bases or. of the diazo salts.

The bases of the" present invention may be alsoIconverted-into diazo-sulfonates. If the basic portion of thesediazo-sulfonates is free from solubilizing groups, they may be blended with appropriate ice-color-coupling components and oxii are meant to be illustrative onlyand not'by-way of limitation. All parts are by weight unless otherwise noted.

Example 1 63 partsof 2-chloro-5-nitrobenzene sulfondir' ethylamide are refluxed for '24 hours with'..27.9

dizing agents. Such blendsmaybe incorporated into a printing paste, printed on vegetablefibers parts of 6-amino- ,3-benzodioxan in 200 parts of water containing 11 parts of calcium carbonate.

.1011 cooling, the precipitatedmaterial is separated by filtration and the residue extracted with hot alcohol. :Upon cooling the alcohol extract, yellow crystals of N (2-sulfondiethylamide-4'-ni- Example 2 20.4-partsof the nitro compound of Example 1 arereduced at reflux temperature in a solution containing 36 parts of sodiumsulfide dissolved in a mixture of 120 parts of alcohol and 50 parts of water. mixture is poured on ice and the white precipi- After 3 hours, the yellowish reaction tated material is collected by filtration. The

phenyl) 56 amino 1,3 benzodioxan melts at 10 1.5-102.5 C. and has the followingstructure:

' Example 3 1 part of the amine produced in Example 2 is treatedwith a solution of 1.65 partsof 31.5% hydrochloric acid in 13.65 parts of water at a.

temperature of 20 C. and then diazotized by the addition of 0.19 part of sodium nitrite in 5 parts of water. After stirring for minutes, 60 parts of water is added and stirring is continued until solution of the diazonium chloride is complete.

This solution is then buffered with sodium acetate solution to a basic test on Congo red paper'and then diluted to '100 parts with water.

:The resultant solution is employed at room tem- Example 4 7.54 parts of the amine as producedin Example 2 are dissolved in20 parts of acetone and this solution is rapidly added to asolution of 60 partsof. zincchloride dissolved in 60 part of water at a temperature of C. At this point,

1.52 parts of sodium nitrite dissolved in 10 parts of .water are slowly added. The precipitated material is filtered, the residue is extracted twice with warm water, the extracts are combined with the first filtrate and the zinc chloride double salt of the diazonium chloride is separated by saturating the solution with salt. Three parts of this dried zinc chloride double salt are intimately mixed with 1.2 parts of magnesium sulfate dihydrate. 2.5 parts of this salt mix are dissolved in 26.5 parts of water containing 0.5 part of sodium acetate and 0.5 part of acetic acid solution. Seventy parts of a carbohydrate thickener are added and the color paste is printed on cotton cloth previously impregnated in an alkaline bath containing the alpha-naphthyl-amide of 2- hydroxy-B-naphthoit; acid. The printed fabric is dried, rinsed in a dilute sodaash bathat C. and soaped at the boil. The pattern is printed a strong violet to purple shade.

. Example 5 11.3 parts of the a mineproduced as Example 2 are treated in a solution of 32.6 parts of 17% hydrochloric acid and 30 parts of watenwith.

2.1 parts of sodium nitrite dissolved in 50 parts of water. Some solid material is filtered off, the residue being washed with water. The filtrate is carefully neutralized with sodium carbonate until the solution is just basic to Congo red test paper after which sodium chloride is added and the precipitated, yellow diazonium chloride collected by filtration. Four parts of thedried diazonium product N (2. sulfondiethylamide -4 amino- 1 chloride are dissolved in 250 parts of water and 2 parts of neutral sodium sulfite in 16 parts of water. are added. To the clear solution is added sodium chloride and the sodium diazosulfonate whichlprecipitates is collected by filtration. 2.95 parts of this dried sodium diazosulfonate arcintimately mixed with-1.58 parts of the anilide 0f 2-hydroxy-3-naphthoic. acid. 2.5 parts of this dry color mix are dissolved in 25.5 parts of water containing 0.5 part of sodinmchromate and parts of suitable. carbohydrate thickener are added. The color paste is printedori boiled out cotton cloth, the printed stripe dried and the color developed by steaming. The printis rinsed, treated in 2% soda ash solution at 60 (3., and finally soaped at the boil. The pattern is .dyed

a violet shade. i 1

Example 6 A number of other amides were substituted for the sulfon-diethylamide .of Example 2 and the procedures of Examples 4 and 5 are repeated.

New color formulations are obtained having unusual color value and good general properties. Il-[ lustrative results are set forth in the following table:

Melting Melting Ar point point Y M; nitro I ammo ggfigi Color of dyeing comcomacid i pound pound 1 C. I Amide 199-200 194-195. Anilidenn, Bluc-red shade. Morpholida. 181-182 182-183 do. Strong violet. Diethanol- 1 amidelmh 156-157. do. Deep purple. Anilide 177-178 141-142 do D0. o-Anisidide. 151-152 158-160 a-naphthyl- Violet purple.

amide.

oil. l 1 Example 7;

mixture is then coo-led, the reaction product settled out and the supernatant liquid decanted.

After extraction with dilute hydrochloric acid and alcohol, a yellow, crystalline, residue .of

N- (2-benzoyl-4-nitro-phenyl) 6 amino-1,3-

benzodioxan obtained which on recrystallization from alcohol melts at 142-143 0..

Example 8 p 1 7 parts of the nitro compound of Example 7 is slowly added to a boiling mixture of 10 parts of aqueous sodium sulfhydrate (30%) and 20 parts of alcohol. When reduction is complete, IOO'parts of water are added and the precipitated material removedb filtration. On slurrying withdilute hydrochloric acid, the free base is converted to a 6-amino-L3-benzodioxan.

hydrochloride which is collected by filtration.

base is obtained) It melts a't 163-l5{l'C. and has the following formula:

- HiN Example 9- 013 part of the 'amine'asi prepared in Example 8 are stirred 'in10 parts of water, treated with 1.1 parts of 5 norma1 hydrochloric acid and diazotized by addition of 0.084'part of sodium nitrite dissolved in 5 parts of'water. On completion of diazotization, 30pa rts of water are added and the solution is clarified. 25parts of the diazo'solution so obtained are, treated with 10% sodium acetate solution toanegative acid test against Congo red paper and then'with 5% sodium bicare bonate solution tov a neutraltest to litmus paper.

7 Water is added to a totalof 100'parts and cotton cloth,'previously impregnated in alkaline solution of the anilide of, 2ehydroxy-3 naphthoic acid, is

eaararms Tadded and the undissolved material is filtered ofl.

When the hydrochloride is neutralized, the free amino-1,3-benzodioxan produced according. to

Acidification of the'filtrategwith hydrochloric vacid,'produces a white precipitate which is filtered ofi, washed with ice water. and dried at 455C. 'The product, N4 -sulfo-4-amino=phenyl) -6- amino-1,3-benzodioxan, is a white "solid readily soluble in alkaline'solution. i i

Example '12 1.6 partsof N-(2'-sulfo-4'-amino-phenyl)--6- Example 11 is stirred in 35 parts of water and dissolved by the addition of asolution of 0.2 part of sodium hydroxide in parts of water. The

hydrochloride is precipitated in finely-divided form by, running in 2.46 parts of 37%. hydrochloric acid. After lowering the temperatureof the slurry to 5 C., diazotization is accomplished .by adding slowly 035 part of .sodium' nitrite dissolved in 5 parts of water. 'An apple-green slurry results. 3.2 parts of 5,5-dihydroxy-2,2-dinaphthylamine-Tlfl'-disulfonic acid (41.7%) are dissolved in 40 parts of'water containing 2.7 parts of sodium carbonate, the temperature of the solution is adjusted to about 5 C. and the diazo slurry poured in while agitating efiiciently. Coupling is complete within one-half hour, yielding a deep blue solution. The temperature is then raised to padded in this bath. The resulting dyeing. is

. rinsed, heated at the boilin 5% soda ash solution and soaped at elevatedtemperature. A deep purple dyeing results.

Example 10 f is filtered off and washed with ice water on the filter to remove residual potassium chloride.

Example 11 35.0 parts or the saltobtained in Ex m le 10 are slurried in 81 partsof water at 50 C. While agitating efii ciently"; 81 parts; of sodium sulfhy drate' solution (38% aqueous solution) are run in during one-half hour. After heating the resultant "clear red solution for about hour at 50 C., and three hours at 65 9,, the Solution is treated with 30.0 parts of potassium chloride. The temperature of the resulting slurry is lowered to 5 C. and the precipitated product separated by filtration and washed on the filter with a little cold potassium chloride. 1 The residue is slurriedin 250 parts of'water and hydrochloric acid (1.19) is added until the solution shows an acid reaction, to Congo red paper. After stirring for /2 hour;- soda ash is added until the solution is basicto brilliant yellow paper, charcoal is 80 C- and 30.0parts of sodium. chloride added.

After lowering the temperature to 20 C., the precipitated dyestuff is collected on the filter and is driedat 55 C... The dark powder resultingreadily dissolves in water yielding a deep, blue solution of reddish'shade.

Ewqlmple 13 t =0;5-p art of the dyestuffasobtained inEXample 12 is dissolved in 500 parts of Water. 50 parts of this solution are diluted with 250 paItsof'Water' and then 3.5 parts of 10% Glaubers salt and1L0 part of- 10% sulfuric acid are added. Five parts of woolen flannel are well boiled out in 1%-soap solution, rinsed in fresh water and entered into this dye bath. The temperature is raised to the boil and maintained thus for one hour while the woolen piece goods is Wellagitated After'renioval from-the dye bath, the wool is 'rins'ed 'in hot water, soaped at 65 C., rinsed again and finally dried. It is levelly'dyed a royal blue of distinctive brightness. i

Emmpleu f for one .hour and .the cotton piece goods'is re moved. It is rinsed, treated at 65 C'. in 1% soap solution, again rinsed and dried. An extremely bright blue dyeing of marked greenish shade resulted. 1

Errample 1 5 fDy'estulfs of distinctive colors valuable because of brightness and general fastness properties are 7 obtained by diazotization ofthe bases of the present invention and. coupling of the resulting diazo compounds with a variety of coupling com ponents. The following list illustrates vsome of the dyestuffs obtainable and the shades produced from their application: j

1. New azo dyestuffs of the general formula A---N=l T-B in which A is the residue of a coupling component and B is the residue of an N para-amino-phenyl 6-amino-1,3-benzodioxan.

2'. New azo dyestuffs of the general formula AN=N-B in which A is the residue of an icecolor coupling component and B is the residue of an N-para-amino-phenyl 6- amino-1,3-benzodioxan. V

3. New azo dyestuifs of the general formula A-N=N-B in which A is the residue ofan arylide of 2 hydroxy-3-napthoic acid, and B is the residue of an N-para-amino-phenyl G-amino .1;3-pbenzodioxan.

4. New azo dyestuffs of the-general formula A--N=N-B in which A is the residue of an icecolor coupling component and B is the residue of a 2-substituted N-para-amino-phenyl 6- amino-1,3-benzodioxan.

5. An azo dyestuff according to claim 4 in which A is the residue of an arylide of Z-hydroxy- 3-naphthoic'acid. i l

6. An azo dyestufi having the formula in which A is the residue of an ice-color coupling component. i v

7. An azo dyestuff according to claim 6 in which Acid wool Dlrect cotton Dyestuffs Color of dye dyeing dyeing N a( 2-sullo-4'-aminophenvl) -6-amino-1,3-l en- Q-hydroxy naphthalene-3,6-disulfouic acid Purple Corinth. 20 ioxan NW-sulfo-Q-aminophenyl)-6amino-1,3-ben- 2-a(11nino-5-hydroxy-naphthalene-7-sulfonic Red-blue.-- Maroon... zo oxen am 1 N-(2'-sulfo-4-aminophenyl)-6-amino-1,3-ben- 5,5-djhydroxy-ZJGdinaphthy1urea-7,7-di- Royal'blue- Navyblue Navy blue. zodioxan l sulfonic acid p i a N-(fiZsulfo-eieminophenyD-S-amino-l,3-ben- 1-(4'-sulfophenyl)-3-methylpyIazolone-5 Brown-red. Red zo oxen 7 i v I N-(2-sulfo4-aminophenyl)-6-amino-L3-ben- -e 1 amino 8 hhydroxy. napthalene 3,6 di- Purple Blackzodioxan (acid) sulfo nlfi acid p aniline (alkaline) N -(2-sulfo-4-aminophenyl)-6-a1nino-1,3-ben- 2hydroxy benzoic acid Light brown Khaki (to zodioxan p chromed N-(2'-sulfo-4'-aminophenyl)-6-amino-1,3-ben- Aceto acetam'lide Orange Golden zodioxan v l I orange N-(2-su.lfo-4-ami11ophenyl)-6-amino-1,3-ben- 1,3-dihydroky benzene Brown Golden zodioxan (neutral) Tn brown sulfanilic acid (alkaline) N- (2-sulfondiethylamide-4-aminophenyl)- 2-hydroxy naphthalene-3,6- djsulfonic acid.- Violet Purplen" 6-amino-l,3benzodioxan N-(2-sulfonamide-4'-aminophenyl)-6-amino- 5,5-dihydroxy-2,2-d.inaphthylurea-7,7'-di- Corinth Purple. 1,3-benzodioxan sulionic acid N-(2-benzoyl-4'-aminophenyl)-6-amino-1,3- 5,5-dihydroxy-2,2-dinaphthylamine-7,7- Red-blue... Navy blue. benzodioxan I disulfom'c acid N-(2'-sulio-4-aminophenyl) -6-amino-1,3-benl-naphthylamine zodioxan (diazotized) J, i

r l-naphthylamine-7-sulfonic acid .L (diazotized) Green-blue. N phenyl 5 hydroxy 2 -naphtl1ylamine 7- sulfonic acid We claim: A represents the residue of an arylide of 2-hydroxy-e-naphthoic acid.

8. An azo dyestuif havingthe formula 02H: i in which Ais the residue of an ice-color coupling component. l V

11. An azo dyestuff according to claim 10in which A represents the residue of an arylide of 2-hydroxy-3-naphthoic acid.

i HANS Z. LECHERF JOHN P. GOULDING.

ROBERT P. PARKER. 

